Copolymers of aziridine compounds



United States Patent 3 355 437 COPOLYMERS 0F kzfiuDINE COMPOUNDS Giuliana C. Tesoro, Dobbs Ferry, N.Y., and Kelvin B. Domovs, Newark, NJ., assignors to J. P. Stevens & Co.,

ABSTRACT OF THE DISCLOSURE The process of, and the product formed 'by, reacting at least two aziridinyl monomers, one of the aziridinyl monomers embodying at least one aziridinyl group of one basicity type which has a radical other than hydrogen attached to the aziridinyl nitrogen; and the other of the aziridinyl monomers being polyfunctional with respect to aziridinyl groups, at least two of the aziridinyl groups of the last-named monomer being of different basicity type than the aziridinyl group of said first-named monomer and having a radical other than hydrogen attached to the respective aziridinyl nitrogens.

Also the co-reaction of the above-mentioned aziridine monomers with functional groups capable of reacting with the aziridinyl groups of the monomers, such as epoxides, amines, amides, isocyanates, mercaptans, phenols, reactive halides, alkylating agents and hydroxymethyl phosphones.

This is a continuation-in-part of our co-pending patent application Ser. No. 293,199, filed on July 5, 1963 now abandoned.

This invention relates to new copolymeric materials and more particularly to materials obtained by copolymerization of aziridine compounds.

The polymeric materials of this invention are the reaction products of at least two aziridinyl monomer compounds which diifer in the basicity of the respective aziridine nitrogens, the difference in basicity being determined according to the Lowry Bronsted definition of acids and bases where a base is a proton acceptor and the more basic compound is one which has a greater tendency to accept the protons, regardless of pH, with at least one of the aziridinyl monomers being at least bifunctional with respect to the aziridine radicals. The aziridinyl compounds with which this invention is concerned have a group other than hydrogen attached to the aziridine nitrogen.

Reactions between two aziridinyl monomers of the same basicity where one is bifunctional produce no distinct interaction. Thus it is essential that the tWo monomers have aziridinyl functional groups of different basicities. 60 The 'bifunctional character is believed to be necessary in order to obtain cross-linked 3-dirnensional polymers.

Among the types of aziridinyl functional groups which may be embodied in the monomers which form the initial Patented Nov. 28, 1967 reactants for the copolymers of this following shown in Table I below:

invention are the TABLE I Type of Azin'dinyl Functional Group (1) Amine (2) Carham ate O (3) Carboxamide J-( JN B (4) Carbamide or thiocarbamide lIIC-N (5) Phn nhm-amidn *X is oxygen or sulfur.

In Table I above, the notation:

is intended to have the following structural meaning:

where R is selected from the group consisting of hydrogen and lower alkyl radicals having from one to five carbon atoms.

The seven types of aziridinyl functional groups shown in Table I have differing basicities, one from the other, by reason of the structure of the group, specifically the I manner of attachment to the aziridinyl nitrogen. These 3 4 this invention are shown in Table II below. In Table II, the monomers are grouped according to the manner of I above. For each monomer, the degree of functionality with respect to aziridinyl functional groups is also inattachment of the aziridinyl nitrogen, as typified in Table dicated.

TABLE II Reference Formula Type Function- Code ality [A] DNCHnCHzSOzCHzCHzNj (1) 2 [-B] I NCH (|3H CHGHzN (1) 2 CH; OH;

I! I [C] N -CIZH.HO HzC-O (CHmO 37C11 H-Nj ('1) 2 CH CH [D] N-ECHzCHzOiOHzCHzNi] (1) 2 (wherein X is an integer between 1 and 50) [E] N-CHzCH 1 1 OH; (I? 0 CH3 [F] /NCO C HI CH;,O i k-N 2 2 CH1: (I? I? OH: [G]. \SI:C(CH;)4.O-N I (3) 2 El) CH; (3) 2 i N-C (\H: H QH: N CN II I! [J] /N 'NH( H2)eNHNj (4) 2 [E1 CHzOHgCHNHi'Z'l-Nj 4 1 N P 5" J: 3

[ I: N H 5 I Ggrl LN] 'NEPO l l 3 {QIZT'P'ZIT' 2 N N \Y N /.v

Reference Formula Type Function- Code ality N CH; [Q1 [I =t t=i l w 6 (H41: N N

L CH.

See Table I for Key to Type.

From the above it will be seen that for example the reaction of monomers [E] and [K] is not included as part of the invention unless another monomer from said group is also employed, the reason being that monomers [E] and [K] are only monofunctional with respect to the aziridinyl group and for preparing the copolymers of this invention it is essential that the reaction mixture contain at least one aziridinyl monomer which is at least bifunctional with respect to aziridinyl grouping.

The functionality of the monomers with respect to aziridinyl functional groups can range from unity up wards. In the monomers of Table H which are polyfunctional, e.g. have a functionality greater than unity, all of the aziridinyl groups are of the same basicity. In other words, the monomers which are polyfunctional contain aziridinyl groups of one type only. It is to be appreciated that polyfunctional monomers which contain aziridinyl groups of different type are also suitable for purposes of this invention.

The basic reaction of the present invention involves the use of two monomers, each containing aziridinyl functional groups. One of the monomers must embody at least one aziridinyl group. The other monomer must embody more than one aziridinyl group, tag. it must be polyfunctional with respect to this group; and at least two of the aziridinyl groups must be of different basicity type than the group embodied in the first monomer.

In carrying out the polymerization reactions of the present invention, it is desirable, although not necessary, to employ elevated temperatures. Temperatures above 180 C., however, are not generally desirable. Pressure may be varied-over wide ranges and the reactions may be carried out at atmospheric, super-atmospheric or sub-atmospheric pressures. The monomers can be added together in any'desired sequence and they may be combined in any desired ratio, although the ratios of the various monomers will to an extent determine the yield and properties of the resultant polymer. It is possible to withhold a portion of one or more of the monomers and subsequently complete the polymerization reaction by introducing an additional monomer. One or more monomers may be added entirely or in part subsequent to an initial pro-polymer formation. Reactive components may also be grafted to another previously formed polymer provided such polymer contains reactive sites capable of combining with at least one of the aziridine monomers.

The monomer mixture may contain other substances such as diluents, solvents, filler, polymerization accelerators or retarders in addition to the two aziridiny-l monomers. The use of solvents is desirable in some instances although not necessary. Additional reactants can also be employed in order to modify the structure of the copolymer formed. Such coreactants should contain functional groups capable of reacting with the aziridinyl groups of the essential comonomers. Among these are, for example, epoxides, amines, amides, isocyanates, mercaptans, phenols, reactive halides, alkylating agents, hydroxymethyl phosphines and the like.

Among the preferred coreactants are the following:

Catalysts are not necessary in carrying out these polymerization reactions, although they can be used as accelerators to initiate the polymerization reaction. Any acidic or acid-forming compound can be used as a catalyst.

The time required to form a gel may be taken as an indication of the polymerization rate. It is not necessarily identified with it, although it is generally related to it. Thus the time required to form a gel is a useful indication of the reactivity of the system. High reactivity is generally desired. The presence of diluents and inert solvents generally decreases the rate of reaction and hence provides a useful =means for controlling the polymerization.

The polymeric materials produced by this invention are resinous and rubbery infusible or thermoplastic solid materials having physical and chemical properties which make them useful as textile, paper and leather finishes, dye fixation agents, ion exchange absorbents, binders, adhesives, protective coatings, and materials of construction.

For a more detailed understanding of this invention, reference should now be made to the following examples which are illustrative of this invention. Obviously many modifications will be apparent to those skilled in the art and applicants intend to be bound only by the spirit and scope of the appended claims.

In the following examples the yield was determined from the weight of the insoluble gelled product which was determined by washing each comrninuted gel by decantation at least five times with methanol and drying it at C. At least 20 hours elapsed between successive decantations to allow time for diffusion from the interior of the gel of the larger particles. Yield is expressed as a percentage of the total weight of reactant.

In these examples the reference to heating for a period of 15" times the gel time was an arbitrary way of assuring that the reaction proceeded to essential completion.

EXAMPLESREACTIONS BETWEEN AMINE (1) AND CARBAMATE (2) Example 1 Monomer [B] and monomer [F] were mixed in vari- 7 ous proportions and heated to 93 C. The time at which each mixture began to gel was as follows:

Percent [B] 80 Minutes ng ng 50 33 27 30 38 53 84 140 ng The ternary mixture of 25% of monomer [C], 25% of monomer [B] and 50% of monomer [F] gelled in 12 minutes at 130. Heated 30 minutes, it was tough, flexible and colorless. The methanol-insoluble yield was 42% of polymer having a dye absorption value of 4.0 meq./ g. A similar mixture gelled in about 40 minutes at 100 C.

The Dye Absorption Capacity=meq. of Orange II Acid 1 absorbed per gram of polymer.

The Dye Absorption Capacity was determined by the following test:

To about 0.2 g. of isolated gel, 2.0 ml. of glacial acetic acid were added, fol-lowed by a measured excess of 0.04 N aqueous Orange II Acid. After a week at room temperature, with occasional shaking, an aliquot of the supernatant liquid was analyzed color-metrically at 4850 Angstrom.

Example 3 A mixture of 47% of monomer [B], 20% of monomer [F], and 33% of coreactant [X] yielded a rubbery, yellowish gel in about 600 minutes at 25 C. The dye absorption value of the resin was 6.1 meq./ g. The yield was 8 REACTIONS BETWEEN CARBAMIDE (4) AND CARBAMATE (2) Example 6 Several suspensions of the solid monomer [J] in various proportions of monomer [F] were heated to C., at which temperature homogeneous solutions formed, for about ten times the gel time, as follows:

Percent [.T] at start 79 60 Minutes to gel 20 21 Percent yield 93 89 Percent Nitrogen found- 19. 0 17. 5 Percent [J] in copolymer 69 53 The nearly invariant gel time occurring with proportions of [I] between 60 and 100% is noteworthy, as well as the ability of [F] to gel in the presence of a minor fraction of [I] but not in the absence of [J]. This behavior contIasts with that of [I] when mixed with an inert solvent such as tetraglyme (tetraethylene glycol dimethyl ether) instead of [F]. Tetraglyme in minor proportions raises the gel time, and at proportions of 5 0% and greater causes precipitation instead of gelation.

Example 7 A mixture of equal parts of monomer [F] and monomer [G] yielded a thermoplastic solid in 480 minutes at C., while the two components, heated separately, remaine liquid of increased viscosity.

Example 8 With equal parts of monomer [F], [H] and the solvent o-dichlorobenzene, a weak gel formed in 30 minutes at 100 C.

REACTIONS BETWEEN AMINE (1) AND CAR- BAMIDE (4) Example 9 The heating of several mixtures of monomers [B] and [K], neither of which gels by itself, showed that with about equal weights of the two, maximal reaction rate, yield and strength resulted as follows: 7

Percent [K] 13 25 47 78.

Gel tnn e and temperang ng 152 min. at 100--- 520 min. at 100 tum C. +20 min. at 130.

Properties when cold Liquid.-- L1qu1d Strong Weak.

Percent yield 72 30.

Example 4 Percent [Z] 0 10 Min. to gel at 130 C 4 Similar results were found in the following copolymerization experiments:

9(a). [B] and [J] at 115 C. 9(b). [A] and [J] at 121 C.

REACTIONS BETWEEN AMINE (7 AND PHOSPHORAMIDE (5) Example 10 Mixtures of monomers [B] and [L] were heated at 100 C. for ten times the gel time of each with the following results:

[Z] raised both the rate of reaction and the flexibility of the resin obtained. With 10% of [Z], the gel retained great toughness and formed a strong bond to glass. With 30% of [Z], the copolymer was a tacky rubber.

Similar results were found in the following copolymerization experiments:

5(a). [E] and [F] at 100 C. 5(b). [D], wherein X is about 12, and [F] at 130 C. 5(c). [A] and [F] at 121 C.

p (2-hydroxy-1 naph'thylazo) benzene sulfonic acid.

Percent [L] 0 23 49 79 100. Mm. to gel ng 70 19 12 114. Gel strength Fluid Very weak Strong Strong Weak. Percent yield- 0 71 9s 81 Thus, with about 50% of [L], maximal reaction rate, yield and strength were obtained.

Similar results were found in the following copolymerizations:

10(a). [B] and [M] at 130 C. 10(b). [B] and [N] at 130 C.

9 10(0). [B] and [O] at 100 C. to 130 C. 10(d). [A] and [L] at 121 C.

REACTION BETWEEN AMINE (1) AND CYANURAMIDE (6) Example 11 Monomer [P] was suspended in Various proportions in monomer [B] and heated at 100 C. While [P] by itself failed to gel, possibly because it did not melt before polymerizing, and while [B] remained fluid, mixtures of the two became firmly cemented masses.

Percent [P] Min. to gel at 100 REACTIONS BETWEEN PHOSPHONITRILAMIDE (7) AND PHOSPHORAMIDE Example 12 Mixtures of [Q] and [L] showed distinct interaction during polymerization, as follows: (each was heated for ten times the gel time).

Percent [Q] 0 1s 50 82 100 Min. to gel at 130 12 9.5 11 11 21 Percent yield- 1 62 88 59 62 This yield was determined on a second sample heated at 115 instead.

lEteacted violently with some decomposition 0.5 minute after gelling.

REACTIONS BETWEEN AMINE (1) AND CAR- BOXAMIDE (3) Example 13 With mixtures of monomers [B] and [G], maximal reaction rate and strength were found at concentrations of [G] between about 20% and 40%. All these gels were less rigid than the strongest gels made from [B] and [F] (Ex. 1). The gelation of [B] and [G] proceeded as follows:

Equal parts of monomers [B], [I] and tetraglyme solvent yielded a tough amber rubber in about 60 minutes at room temperature. After it had remained standing for two days, extraction by methanol left a 79% yield of polymer having a dye absorption capacity of 4.0 meq./ g.

Substitution of additional tetraglyme for all the [B] of the above formulation gave much inferior gelation.

Example 15 A solution of 32 parts of monomer [H] and 36 parts of hot o-dichlorobenzene was cooled and mixed with 31 parts of monomer [B]. Within 60 minutes at 25, a tough green gel formed which later turned amber and got still tougher. After it had stood for two days, its extraction with methanol left an 89% yield of gel.

At 100 C., equal parts of monomer [H], [B] and 1'0 orthodichlorobenzene formed within two minutes a tough gel which could not be pried from the reaction tube.

REACTIONS BETWEEN AMINE (1) AND PHOSPHONITRILEAMIDE (7) Example 16 Gels were formed by heating mixtures of monomers [B] and [Q] at 100 C. as follows:

Percent [Q] 25 52 83 100 Min. to gel at 100 0 ng 400 400 280 Gel character 1 Soft when cold. 2 Tough cold. soft at 100.

REACTIONS BETWEEN CARBAMIDE (4) AND CARBOXAMIDE (3) Example 17 I Mixtures of monomers [I] and [G] gelled as follows:

Percent [J] 100 91 81 71 60 4o 11 0 Min. to gel at 117 0 17 a0 43 57 89 420 540 ng REACTIONS BETWEEN CARBAMATE (2) AND PHOSPHONITRILAMIDE (7) Example 18 Mixtures of monomers [F] and [Q] gelled at 130 C. as follows during a total heating time of 300 minutes for each.

Percent [Q] 0 19 50 79 85 Min. to gel 11g 230 250 230 135 21 Percent yield '0 28 6 4:0 63 1 62 1 This yield was determined on a second sample heated instead at C. for 600 minutes, ten times its gel time.

Copolymers formed with a wide range of compositions though no maxima in rate or. yield were found for any mitxure.

REACTIONS BETWEEN CARBAMATE (2) AND AND PHOSPHORAMIDE (5) Example 19 Mixtures of monomers [F] and [L] with a broad range of compositions gave high yields of gels at C., as follows (each was heated minutes):

Percent [L] 0 24 48 75 88 100 Min. to gel ng 40 25 16 16 12 Percent yield 0 78 90 100 100 Example 20 Percent [M] 0 10 40 67 82 100 Min. to gel 11g ng 100 100 120 80 Percent yield 0 0 54 63 64 Example 21 The following copolymers, prepared as in Example 1, were tested for their total hydrochloric acid exchange capacity and their absorption capacity for the acid form of the dye Orange 11:

Percent [B]- 33 50 67 33 Percent [F] 67 50 33 33 Percent Tetraglym 0 0 34 Min. to gel at 130 6 8 15 Gel strength Tough Vtery h Tough Weak oug Perceilfi) yielctL .6 -415 55 80 73 91 Dye sorp ion apacity (meq/g. 3. 4 1. 7 0.9 0.9 Acid Exchange Capacity Hp 3. 1 2. 6 3. 6

Example 22 Starting with a free-flowing mixture of 2 parts of monomer [B] and 3 parts of monomer [F] an eleven ply 0.128 inch laminate was made with heat cleaned fiberglass fabric treated with Volan A, cured at 93 for 120 minutes, and post-cured at 177 for 60 minutes. The dry fiexural strength was 74,900 p.s.i. and after an eight hour boil in water the dry flexural strength of the laminate was still 62,500 p.s.i. The flexural modulus of elasticity was 2.2)( p.s.i. dry, and after an eight hour boil it was 1.8)(10 p.s.i. The hardness of 60 (Barcol test), the dielectric constant of 4.35, and the dissipation factor of 0.0109 like the strength and modulus, were in the range of these values for commercially useful resin-fiberglass laminates.

Good laminates were also made with the same comonomers and other glass fabrics (e.g. cloths finished with epoxy-silane, or amino silanes such as Union Carbide A- 1100 and Dow Corning 6030) and with rovings and nonwoven mats.

The refractive index of the monomer mixture can be adjusted so as to match the refractive index of certain solid fillers or substrates. Thus the 2:3 mixture of monomers [B] and [F] (refractive index=1.488) remained transparent when filled and cured with Cab-O-sil silica or untreated Pyrex glass Wool.

Example 23 A 3:2 mixture of monomers [F] and [B] was applied to shiny aluminum foil as a 10% solution in carbon tetrachloride, dried and heat cured. Though the coating was so thin that ditfraction rings appeared, it prevented any visible attack of the aluminum by drops of 0.2 N hydrochloric acid and sodium hydroxide, respectively, allowed to evaporate on t e surface. Control samples of unprotected surfaces were obviously corroded under these conditions.

The surface of polyethylene was hardened by a thin layer of a 3:2 mixture of [F] and [B] monomers cured on it. Similarly a scratched piece of glass was strengthened and transparentized by having a layer of the same copolymer cured upon it.

By itself, the 3:2 [F]-[B] copolymer, when gradually heated in air,.s1owly turned yellow beginning at 220 C. and black without melting at 290 C. Some condensable vapor was evolved during prolonged heating at 290 C. The same copolymer, compared with an acid-catalyzed homopolymer from [B] showed greatly improved resistance to dilute peracetic acid.

Example 24.:Adhesive Two thin sheets of glass with an interlayer of a 3:2 [FJ-[B] copolymer cured between them gained shatter 12 resistance. Two sheets of Du Pout Mylar polyester likewise was laminated securely.

The same comonomer mixture was used to repair broken porcelain and aluminum apparatus. The latter held a vacuum of one micron. 7

It is to be understood that the proportions and ratios of monomers as expressed in the'foregoing examples and in the claims are parts by weight thereof.

What we claim is:

1. A process of preparing a polymeric material comprising reacting together as the sole polymerizable ingredients at least two aziridinyl monomers which differ in the basicity-type of their respective aziridine nitrogensas evidenced by their having dififerent aziridinyl functional groups selected from the class consisting of amine, carbamate, carboxamide, cyanuramide, phosphonitrilamide and carbamide, said monomers being'selected from the group consisting of wherein X is an integer between 1 and 50 P L E [Rial at least one of said two difierent monomers being at least bifnnctional with respect to the aziridine group, and recovering the desired polymeric material.

2. The polymeric material prepared according to claim 1.

3. The polymeric material prepared according to claim 1 wherein the monomer wherein X is an integer between 1 and 50 is reacted with the monomer C H: C HaNj I) (I NCHzCHaSOaCHzCHgN D 3 NCH2CH CH-CEzN H; CH3

l N-([3HCHzC-O (011940 (Portion-N3 CH3 CH3 [D 1 ECHzCHiO]x CHzCHzN l wherein X is an integer between 1 and 50 t N-CHBCHF [F] CH3 1 H CH;

NCOCH2CH2OCNJ [G] 0113 0 0 CH3 II II (I C(CH:)4C

[H] CH; 0 c1 01 0 CH:

and a co-reactant selected from the group consisting of 01-0Hzi'J-0(0H10Hi0)i;0Hio1 -O--OHz-CHCH2 said aziridinyl monomers and said coreactant being the sole polymerizable ingredients, and recovering the de- 45 sired polymeric material.

6. The polymeric material prepared according to claim 5.

7. The polymeric material prepared according to claim 5 wherein the aziridinyl monomers are selected as [D] 60 and [F].

References Cited UNITED STATES PATENTS 2,272,489 2/1942 Ulrich 260-2 55 2,360,192 10/1944 Bestian 26077.5 2,582,594 1/ 1952 Kropa et a1. 2602 2,626,931 1/1953 Bestian 2602 2,901,443 8/1959 Starck et a1. 260-2 3,162,617 12/1964 Smith 260-775 60 3,223,681 12/1965 Rambosek 260-2 3,225,013 12/1965 Fram 2602 SAMUEL H. BLECH, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,355,437 November 28, 1967 Giuliana C. Tesoro et al.

It is hereby certified that error appears in the above numbered p2 ent requiring correction and that the said Letters Patent should read a corrected below.

Column 1, lines 31 and 32, for "phosphones" read phosphines column 2, TABLE I, second column, the last form should appear as shown below instead of as in the patent:

column 7, lines 35 and 36, for "color-metrically at 4850 Angst read colorimetrically at 4850 Angstroms column 8, line 57, for "(7)" read (l) column 10, line 4, for

"PHOSPHONITRILE'AMIDE" read PHOSPHON'ITRILAMIDE column 11 line 47, for "Cab-O-sil" read Cab-O-Sil column 14, line 12, Equation (K) should appear as shown below instead of as in the patent:

H CH 3CH CH 2NHCN l Signed and sealed this 22nd day of July 1969.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. WILLIAM E. SCHUYLER,JR. Attestlng Officer Commissioner of Patents 

1. A PROCESS OF PREPARING A POLYMERIC MATERIAL COMPRISING REACTING TOGETHER AS THE SOLE POLYMERIZABLE INGREDIENTS AT LEAST TWO AZIRIDINYL MONOMERS WHICH DIFFER IN THE BASICITY-TYPE OF THEIR RESPECTIVE AZIRIDINE NITROGENS AS EVIDENCED BY THEIR HAVING DIFFERENT AZIRIDINYL FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF AMINE, CARBAMATE, CARBOXAMIDE, CYANURAMIDE, PHOSPHONITRILAMIDE AND CARBAMIDE, SAID MONOMERS BEING SELECTED FROM THE GROUPS CONSISTING OF 